Synthesis and characterization of metathesis catalysts

ABSTRACT

This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals, and pharmaceuticals.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/378,791, filed Aug. 24, 2016.

TECHNICAL FIELD

This invention relates generally to olefin metathesis catalysts, to thepreparation of such compounds, compositions comprising such compounds,methods of using such compounds, and the use of such compounds in themetathesis of olefins and in the synthesis of related olefin metathesiscatalysts. The invention has utility in the fields of catalysis, organicsynthesis, polymer chemistry, and in industrial applications such as oiland gas, fine chemicals and pharmaceuticals.

BACKGROUND

Since its discovery in the 1950s, olefin metathesis has emerged as avaluable synthetic method for the formation of carbon-carbon doublebonds. Recent advances in applications to organic syntheses and polymersyntheses mostly rely on developments of well-defined olefin metathesiscatalysts.

The technology of ruthenium metathesis catalysts has enabled thedevelopment of several research platforms including: ring openingmetathesis polymerization (ROMP), ring opening cross metathesis (ROCM),cross metathesis (CM), and ring closing metathesis (RCM).

First Generation Grubbs ruthenium olefin metathesis catalysts, such as:(PCy₃)₂(Cl)₂Ru═CHPh, have been largely used in organic synthesis.

The incorporation of certain types of N-Heterocyclic Carbene (NHC)ligands played an essential role in the development of rutheniummetathesis catalysts, giving rise to the Second Generation Grubbsruthenium olefin metathesis catalysts, such as:(IMesH₂)(PCy₃)(Cl)₂Ru═CHPh, where IMesH₂ is1,3-dimesityl-4,5-dihydroimidazol-2-ylidene.

In order to exchange the phosphine on the Second Generation Grubbsruthenium olefin metathesis catalysts, the Grubbs group reported in 2001(Organometallics 2001, 20, 5314-5318) a method involving a precursorbearing two pyridine ligands: (IMesH₂)(Cl)₂(C₅H₅N)₂Ru═CHPh. The labilepyridine ligands have allowed the preparation of diverse rutheniumolefin metathesis catalysts. However, the preparation of pyridinecomplexes, requires large quantities of expensive and malodorousreagents (pyridine), and difficult reaction conditions (negative ° C.temperatures) especially for industrial scale-up.

Therefore there is an ongoing need for efficient, high yield, highpurity and ease in scaling up procedures for the synthesis of olefinmetathesis catalysts, particularly Second Generation Grubbs rutheniumolefin metathesis catalysts.

SUMMARY OF THE INVENTION

To meet this need the inventors have discovered novel ruthenium olefinmetathesis catalysts, bearing a sulfoxide ligand as described herein.The ruthenium olefin metathesis catalysts bearing sulfoxide labileligands exhibit high stability and allow the ready synthesis of variousSecond Generation Grubbs ruthenium olefin metathesis catalysts in higheryield and with higher purity, compared to the existing procedures.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (I)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group [—S(O)—];

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenolate, thiolate,alkylthio, arylthio, or nitrate; typically, X¹ and X² are independentlyCl, Br, I or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene.

In one embodiment, the invention provides a method of synthesizing theolefin metathesis catalysts of the invention.

In one embodiment, the invention provides a method of using the olefinmetathesis catalysts of the invention in metathesis reactions.

In one embodiment, the invention provides a method of synthesizing aSecond Generation Grubbs catalyst, using an olefin metathesis catalystof the invention.

Other embodiments of the invention are described herein.

These and other aspects of the present invention will be apparent to oneof skill in the art, in light of the following detailed description andexamples. Furthermore, it is to be understood that none of theembodiments or examples of the invention described herein are to beinterpreted as being limiting.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram ofC747.

FIG. 2 depicts an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram ofC647_(m).

FIG. 3 shows the conversion of diethyl 2,2-diallylmalonate to4,4-bis(ethoxy carbonyl)cyclo-pentene in the presence of an array ofruthenium catalysts.

DETAILED DESCRIPTION

Unless otherwise indicated, the invention is not limited to specificreactants, substituents, catalysts, reaction conditions, or the like, assuch may vary. It is also to be understood that the terminology usedherein is for the purpose of describing particular embodiments only andis not to be interpreted as being limiting.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “an olefin” includesa single olefin as well as a combination or mixture of two or moreolefins, reference to “a substituent” encompasses a single substituentas well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “forexample,” “for instance,” “such as,” or “including” are meant tointroduce examples that further clarify more general subject matter.Unless otherwise specified, these examples are provided only as an aidfor understanding the invention, and are not meant to be limiting in anyfashion.

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group, typically, although not necessarily,containing 1 to 30 carbon atoms, generally, containing 1 to 24 carbonatoms, typically, 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, t-butyl, octyl, decyl, and the like, aswell as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like.The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms,and the specific term “cycloalkyl” intends a cyclic alkyl group,typically, having 4 to 8, preferably 5 to 7, carbon atoms. The term“substituted alkyl” refers to alkyl substituted with one or moresubstituent groups, and the terms “heteroatom-containing alkyl” and“heteroalkyl” refer to alkyl in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkyl” and “lower alkyl” include linear, branched, cyclic,unsubstituted, substituted, and/or heteroatom-containing alkyl and loweralkyl, respectively.

The term “alkylene” as used herein refers to a divalent linear,branched, or cyclic alkyl group, where “alkyl” is as defined herein.

The term “alkenyl” as used herein refers to a linear, branched, orcyclic hydrocarbon group of 2 to 30 carbon atoms containing at least onedouble bond, such as ethenyl, n-propenyl, iso-propenyl, n-butenyl,iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl,tetracosenyl, and the like. Generally, “alkenyl” groups herein contain 2to 24 carbon atoms, typically, “alkenyl” groups herein contain 2 to 12carbon atoms. The term “lower alkenyl” intends an “alkenyl” group of 2to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclic“alkenyl” group, typically, having 5 to 8 carbon atoms. The term“substituted alkenyl” refers to “alkenyl” substituted with one or moresubstituent groups, and the terms “heteroatom-containing alkenyl” and“heteroalkenyl” refer to “alkenyl” in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkenyl” and “lower alkenyl” include linear, branched, cyclic,unsubstituted, substituted, and/or heteroatom-containing “alkenyl” andlower “alkenyl,” respectively. The term “alkenyl” is usedinterchangeably with the term “olefin” herein.

The term “alkenylene” as used herein refers to a divalent linear,branched, or cyclic alkenyl group, where “alkenyl” is as defined herein.

The term “alkynyl” as used herein refers to a linear or branchedhydrocarbon group of 2 to 30 carbon atoms containing at least one triplebond, such as ethynyl, n-propynyl, and the like. Generally, “alkynyl”groups herein contain 2 to 24 carbon atoms; typical “alkynyl” groupsdescribed herein contain 2 to 12 carbon atoms. The term “lower alkynyl”intends an “alkynyl” group of 2 to 6 carbon atoms. The term “substitutedalkynyl” refers to “alkynyl” substituted with one or more substituentgroups, and the terms “heteroatom-containing alkynyl” and“heteroalkynyl” refer to “alkynyl” in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkynyl” and “lower alkynyl” include linear, branched, unsubstituted,substituted, and/or heteroatom-containing “alkynyl” and lower “alkynyl,”respectively.

The term “alkoxy” as used herein refers to an alkyl group bound througha single, terminal ether linkage; that is, an “alkoxy” group can berepresented as —O-alkyl where alkyl is as defined herein. A “loweralkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms.Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer toan alkenyl and lower alkenyl group bound through a single, terminalether linkage, and “alkynyloxy” and “lower alkynyloxy,” respectively,refer to an alkynyl and lower alkynyl group bound through a single,terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, directly linked, or indirectlylinked (such that the different aromatic rings are bound to a commongroup such as a methylene or ethylene moiety). “Aryl” groups contain 5to 30 carbon atoms, generally, “aryl” groups contain 5 to 20 carbonatoms; and, typically, “aryl” groups contain 5 to 14 carbon atoms.Exemplary “aryl” groups contain one aromatic ring or two fused or linkedaromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether,diphenylamine, benzophenone, and the like. “Substituted aryl” refers toan aryl moiety substituted with one or more substituent groups; forexample 2,4,6-trimethylphenyl (i.e., mesityl or Mes), 2-methyl-phenyl,2,6-di-iso-propylphenyl (i.e., DIPP or DiPP), 2-isopropyl-phenyl (i.e.,IPP, Ipp, or ipp), 2-iso-propyl-6-methylphenyl (i.e., MIPP, Mipp, orMiPP). The terms “heteroatom-containing aryl” and “heteroaryl” refer to“aryl” substituents in which at least one carbon atom is replaced with aheteroatom, as will be described in further detail infra.

The term “aryloxy” as used herein refers to an aryl group bound througha single, terminal ether linkage, wherein “aryl” is as defined herein.An “aryloxy” group can be represented as —O-aryl where aryl is asdefined herein. Preferred “aryloxy” groups contain 5 to 24 carbon atoms,and particularly preferred “aryloxy” groups contain 5 to 14 carbonatoms. Examples of “aryloxy” groups include, without limitation,phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy,o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy,2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent,and the term “aralkyl” refers to an alkyl group with an arylsubstituent, wherein “aryl” and “alkyl” are as defined herein. “Alkaryl”and “aralkyl” groups contain 6 to 30 carbon atoms; generally, “alkaryl”and “aralkyl” groups contain 6 to 20 carbon atoms; and, typically,“alkaryl” and “aralkyl” groups contain 6 to 16 carbon atoms. “Alkaryl”groups include, for example, p-methylphenyl, 2,4-dimethylphenyl,p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl,3-ethyl-cyclopenta-1,4-diene, and the like. Examples of “aralkyl” groupsinclude, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl,4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl,4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. Theterms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula—OR wherein R is “alkaryl” or “aralkyl,” respectively, as definedherein.

The term “acyl” refers to substituents having the formula —(CO)-alkyl,—(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers tosubstituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or—O(CO)-aralkyl, wherein “alkyl,” “aryl,” and “aralkyl” are as definedherein.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups thatmay or may not be substituted and/or heteroatom containing, and that canbe monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used inthe conventional sense to refer to an aliphatic cyclic moiety, asopposed to an aromatic cyclic moiety, and can be monocyclic, bicyclic,or polycyclic.

The terms “halo,” “halogen,” and “halide” are used in the conventionalsense to refer to a chloro, bromo, fluoro, or iodo substituent.

The term “hydrocarbyl” refers to univalent “hydrocarbyl” moietiescontaining 1 to 30 carbon atoms, typically, containing 1 to 24 carbonatoms, specifically containing 1 to 12 carbon atoms, including linear,branched, cyclic, saturated, and unsaturated species, such as alkylgroups, alkenyl groups, aryl groups, and the like. The term “lowerhydrocarbyl” intends a “hydrocarbyl” group of 1 to 6 carbon atoms,typically, 1 to 4 carbon atoms, and the term “hydrocarbylene” intends adivalent “hydrocarbyl” moiety containing 1 to 30 carbon atoms,typically, 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms,including linear, branched, cyclic, saturated, and unsaturated species.The term “lower hydrocarbylene” intends a “hydrocarbylene” group of 1 to6 carbon atoms. “Substituted hydrocarbyl” refers to “hydrocarbyl”substituted with one or more substituent groups, and the terms“heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer tohydrocarbyl in which at least one carbon atom is replaced with aheteroatom. Similarly, “substituted hydrocarbylene” refers to“hydrocarbylene” substituted with one or more substituent groups, andthe terms “heteroatom-containing hydrocarbylene” and“heterohydrocarbylene” refer to “hydrocarbylene” in which at least onecarbon atom is replaced with a heteroatom. Unless otherwise indicated,the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted asincluding substituted and/or heteroatom-containing “hydrocarbyl” and“hydrocarbylene” moieties, respectively.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbylmolecular fragment in which one or more carbon atoms is replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus, orsilicon, typically, nitrogen, oxygen, or sulfur. Similarly, the term“heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the terms “heteroaryl” and“heteroaromatic,” respectively, refer to “aryl” and “aromatic”substituents that are heteroatom-containing, and the like. It should benoted that a “heterocyclic” group or compound may or may not bearomatic, and further that “heterocycles” can be monocyclic, bicyclic,or polycyclic as described herein with respect to the term “aryl.”Examples of heteroalkyl groups include alkoxyaryl,alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like.Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl,pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl,1,2,4-triazolyl, tetrazolyl, etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,”“substituted aryl,” and the like, as alluded to in some of theaforementioned definitions, it is meant that in the hydrocarbyl, alkyl,aryl, or other moiety, at least one hydrogen atom bound to a carbon (orother) atom is replaced with one or more non-hydrogen substituents.Examples of such substituents include, without limitation: functionalgroups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl,C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—(CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxyl (—COOH), carboxylato (—COO⁻), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CS)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CS)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CS)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CS)—N(C₅-C₂₄ aryl)₂), carbamido (—NH—(CO)—NH₂), cyano(—C≡N), cyanato(—O—C≡N), thiocyanato (—S—C≡N), formyl (—(CO)—H), thioformyl (—(CS)—H),amino (—NH₂), mono-(C₁-C₂₄ alkyl)-substituted amino, di-(C₁-C₂₄alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substituted amino,di-(C₅-C₂₄ aryl)-substituted amino, (C₁-C₂₄ alkyl)(C₅-C₂₄aryl)-substituted amino, (C₂-C₂₄ alkyl)-amido (—NH—(CO)-alkyl), (C₆-C₂₄aryl)-amido (—NH—(CO)-aryl), imino (—CR═NH where R is hydrogen, C₁-C₂₄alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), (C₂-C₂₀alkyl)-imino (—CR═N(alkyl), where R is hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl),where R is hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O⁻), (C₁-C₂₄ alkyl)-sulfanyl (—S-alkyl; also termed “alkylthio”),(C₅-C₂₄ aryl)-sulfanyl (—S-aryl; also termed “arylthio”), (C₁-C₂₄alkyl)-sulfinyl (—(SO)-alkyl), (C₅-C₂₄ aryl)-sulfinyl (—(SO)-aryl),(C₁-C₂₄ alkyl)-sulfonyl (—SO₂-alkyl), mono-(C₁-C₂₄ alkyl)-aminosulfonyl—SO₂—N(H)alkyl), di-(C₁-C₂₄ alkyl)-aminosulfonyl —SO₂—N(alkyl)₂, (C₅-C₂₄aryl)-sulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂),phosphonato (—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), andphosphino (—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferablyC₁-C₁₂ alkyl, more preferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferablyC₂-C₁₂ alkenyl, more preferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl(preferably C₂-C₁₂ alkynyl, more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl(preferably C₅-C₁₄ aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl),and C₆-C₂₄ aralkyl (preferably C₆-C₁₆ aralkyl).

By “Grubbs-Hoveyda ligands,” it is meant benzylidene ligands having achelating alkyloxy group attached to the benzene ring at the orthoposition.

The term “sulfoxide group” refers to —[S(O)]—.

By “functionalized” as in “functionalized hydrocarbyl,” “functionalizedalkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and thelike, it is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin,or other moiety, at least one hydrogen atom bound to a carbon (or other)atom is replaced with one or more functional groups such as thosedescribed herein. The term “functional group” is meant to include anyfunctional species that is suitable for the uses described herein. Inparticular, as used herein, a functional group would necessarily possessthe ability to react with or bond to corresponding functional groups ona substrate surface.

In addition, the aforementioned functional groups may, if a particulargroup permits, be further substituted with one or more additionalfunctional groups or with one or more hydrocarbyl moieties such as thosespecifically enumerated herein. Analogously, the herein-mentionedhydrocarbyl moieties can be further substituted with one or morefunctional groups or additional hydrocarbyl moieties such as thosespecifically enumerated.

“Optional” or “optionally” means that the subsequently describedcircumstance can or cannot occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent can or cannot be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

Olefin Metathesis Catalysts

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (I):

wherein

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenolate, thiolate,alkylthio, arylthio, or nitrate; typically, X¹ and X² are independentlyCl, Br, I, or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (I), wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) and R^(b) are linked together to form a five or a six heterocyclicmembered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenolate, thiolate,alkylthio, arylthio, or nitrate; typically, X¹ and X² are independentlyCl, Br, I, or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (II):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L¹ is a carbene;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene;

X³ and X⁴ are independently O or S; and

R^(x), B^(y), R^(w), and R^(z) are independently hydrogen, halogen,unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R^(x), R^(y), R^(w), and R^(z) are independentlyhydrogen, halogen, unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(x),R^(y), R^(w), and R^(z) are independently C₁-C₆ alkyl, hydrogen,unsubstituted phenyl, substituted phenyl, or halogen; or R^(x) and R^(y)are linked together to form an unsubstituted bicyclic or polycyclic arylor a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) arelinked together to form an unsubstituted bicyclic or polycyclic aryl ora substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (II), wherein:

M is Ru;

L¹ is a carbene;

n is 0;

m is 0;

R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl,cyclohexyl, or phenyl;

R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl,cyclohexyl, or phenyl; or

R^(a) and R^(b) are linked together to form a five or a six heterocyclicmembered ring with the sulfoxide group;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, orsubstituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

X³ and X⁴ are each S; and

R^(x), R^(y), R^(w), and R^(z) are independently hydrogen, halogen,unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstitutedC₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄aryl, or substituted C₅-C₂₄ aryl; typically, R^(x), R^(y), R^(w), andR^(z) are independently C₁-C₆ alkyl, hydrogen, unsubstituted phenyl,substituted phenyl, or halogen; or R^(x) and R^(y) are linked togetherto form an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together toform an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together toform an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (III):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenolate, thiolate,alkylthio, arylthio, or nitrate; typically, X¹ and X² are independentlyCl, Br, I, or F; and

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), N, O, S, or P; only one of X or Ycan be C or CR^(3a); typically, X and Y are each N;

Q¹, Q², R³, R^(3a) and R⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, Q¹, Q², R³, R^(3a), and R⁴ are optionally linkedto X or Y via a linker such as unsubstituted hydrocarbylene, substitutedhydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene,substituted heteroatom-containing hydrocarbylene, or —(CO)—; typically,Q¹, Q², R³, R^(3a), and R⁴ are directly linked to X or Y; and

p is 0 when X is O or S, p is 1 when X is N, P, or CR^(3a), and p is 2when X is C; q is 0 when Y is O or S, q is 1 when Y is N, P, or CR^(3a),and q is 2 when X is C.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (III), wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) and R^(b) are linked together to form a five or a six heterocyclicmembered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenolate, thiolate,alkylthio, arylthio, or nitrate; typically, X¹ and X² are independentlyCl, Br, I, or F; and

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), N, O, S, or P; only one of X or Ycan be C or CR^(3a); typically, X and Y are each N;

Q¹, Q², R³, R^(3a) and R⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, Q¹, Q², R³, R^(3a), and R⁴ are optionally linkedto X or Y via a linker such as unsubstituted hydrocarbylene, substitutedhydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene,substituted heteroatom-containing hydrocarbylene, or —(CO)—; typically,Q¹, Q², R³, R^(3a), and R⁴ are directly linked to X or Y; and

p is 0 when X is O or S, p is 1 when X is N, P, or CR^(3a), and p is 2when X is C; q is 0 when Y is O or S, q is 1 when Y is N, P, or CR^(3a),and q is 2 when X is C.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (IV):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1;

m is 0, 1, or 2;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; or IV and R^(b) are linked togetherto form a five or a six heterocyclic membered ring with the sulfoxidegroup;

X¹ and X² are independently anionic ligands;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹ andR² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), or N; and only one of X or Y canbe C or CR^(3a);

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl;

Q is a two-atom linkage having the structure—[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or [CR¹¹═CR¹³]—;

R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl;

“s” and “t” are independently 1 or 2;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl.

In one embodiment of Formula (IV), any two or more of X¹, X², L², R¹,and R² are optionally linked together to form a cyclic group, includingbidentate or multidentate ligands; or any one or more of X¹, X², L², R¹,and R² is/are optionally attached to a support.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (IV):

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenolate, thiolate,alkylthio, arylthio, or nitrate; typically, X¹ and X² are independentlyCl, Br, I, or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl, or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), or N; only one of X or Y can be Cor CR^(3a); typically, X and Y are each N;

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl;

Q is a linker, typically, unsubstituted hydrocarbylene, substitutedhydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, orsubstituted heteroatom-containing hydrocarbylene; generally, Q is atwo-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or[CR¹¹═CR¹³]—; typically, Q is —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—, whereinR¹¹, R¹², R¹³ and R¹⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; typically, R¹¹, R¹², R¹³ and R¹⁴ are independentlyhydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl,unsubstituted C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl,unsubstituted C₅-C₁₄ aryl, or substituted C₅-C₁₄ aryl; “s” and “t” areindependently 1 or 2; typically, “s” and “t” are each 1; or any two ofR¹¹, R¹², R¹³, and R¹⁴ are optionally linked together to form asubstituted or unsubstituted, saturated or unsaturated ring structure;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), (C₅-C₂₄aryl) substituted with up to three substituents selected fromunsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstitutedC₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl,substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substitutedC₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl, or2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), or (C₅-C₂₄aryl) substituted with up to three substituents selected fromunsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstitutedC₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl,substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substitutedC₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl, or2-methyl-phenyl; or when X is CR^(3a), then R^(3a) and R⁴ can formtogether a five to ten membered cycloalkyl or heterocyclic ring, withthe carbon atom to which they are attached.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (IV), wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) and R^(b) are linked together to form a five or a six heterocyclicmembered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenolate, thiolate,alkylthio, arylthio, or nitrate; typically, X¹ and X² are independentlyCl, Br, I, or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl;typically, R¹ is hydrogen and R² is unsubstituted phenyl, substitutedphenyl or substituted 1-propenyl; or R¹ and R² are linked together toform an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), or N; only one of X or Y can be Cor CR^(3a); typically, X and Y are each N;

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl;

Q is a linker, typically, unsubstituted hydrocarbylene, substitutedhydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, orsubstituted heteroatom-containing hydrocarbylene; generally, Q is atwo-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or[CR¹¹═CR¹³]—; typically, Q is —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—, whereinR¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; typically, R¹¹, R¹², R¹³ and R¹⁴ are independentlyhydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl,unsubstituted C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl,unsubstituted C₅-C₁₄ aryl, or substituted C₅-C₁₄ aryl; “s” and “t” areindependently 1 or 2; typically, “s” and “t” are each 1; or any two ofR¹¹, R¹², R¹³, and R¹⁴ are optionally linked together to form asubstituted or unsubstituted, saturated or unsaturated ring structure;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), (C₅-C₂₄aryl) substituted with up to three substituents selected fromunsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstitutedC₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl,substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substitutedC₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄alkaryl, and halide; typically, R³ is adamantyl, 2-iso-propyl-phenyl,2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), or (C₅-C₂₄aryl) substituted with up to three substituents selected fromunsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstitutedC₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl,substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substitutedC₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl,2-iso-propyl-phenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; or R^(a) and R^(b) are linked together to form a five or asix heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F;

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; or R¹ and R² are linked together to form an optionallysubstituted indenylidene;

X and Y are each N;

Q is —(CH₂—CH₂)— (i.e., a two-atom linkage having the structure—[CR¹¹R¹²]_(s)[CR¹³R¹⁴]_(t)—; wherein R¹¹, R¹², R¹³, and R¹⁴ areindependently hydrogen; and “s” and “t” are each 1);

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide.

Therefore, the olefin metathesis catalyst of Formula (IV) can also berepresented by the structure of Formula (V):

wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; typically, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; typically, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

R^(a) and R^(b) are linked together to form a five or a six heterocyclicmembered ring with the sulfoxide group; typically, R^(a) and R^(b) arelinked together to form a tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; or R¹ and R² are linked together to form an optionallysubstituted indenylidene;

R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl;

R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; or IV and R^(b)are linked together to form a five or a six heterocyclic membered ringwith the sulfoxide group;

X¹ and X² are independently halogen;

R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to threesubstituents selected from C₁-C₂₀ alkyl, substituted unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; and

R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to threesubstituents selected unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl,unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl,substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substitutedC₆-C₂₄ alkaryl, and halide.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is unsubstituted phenyl, substituted phenyl, or substituted1-propenyl;

R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, orphenyl;

R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, orphenyl; or IV and R^(b) are linked together to form atetrahydrothiophene oxide;

X¹ and X² are each Cl; and

R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;and

R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is phenyl, 2-iso-propoxy-phenyl (i.e.,

or 2-methyl-1-propenyl (i.e., —CH═C(CH₃)₂ or

or R¹ and R² are linked together to form 3-phenylinden-1-ylidene (i.e.,

R^(a) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, or phenyl;

R^(b) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, or phenyl;

X¹ and X² are each Cl;

R³ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, adamantyl,2-iso-propyl-phenyl, 2-methyl-phenyl, or 2-isopropyl-6-methyl phenyl;and

R⁴ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-phenyl, 2-methyl-phenyl, or 2-isopropyl-6-methyl phenyl.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R²are linked together to form 3-phenylinden-1-ylidene;

R^(a) and R^(b) are linked together to form with the sulfoxide group atetrahydrothiophene oxide;

X¹ and X² are each Cl;

R³ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, adamantyl,2-iso-propyl-phenyl, 2-methyl-phenyl, or 2-isopropyl-6-methyl phenyl;and

R⁴ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-phenyl, 2-methyl-phenyl, or 2-isopropyl-6-methyl phenyl.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (V), wherein:

R¹ and R² are linked together to form 3-phenylinden-1-ylidene;

R^(a) is methyl;

R^(b) is methyl;

X¹ and X² are each Cl;

R³ is 2,4,6-trimethylphenyl; and

R⁴ is 2,4,6-trimethylphenyl.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (V) are described in Table (1), wherein X¹ is Cland X² is Cl.

TABLE 1 Catalyst R¹ R² R³ R⁴ R^(a) R^(b)  1 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ MeMe  2 H Ph Mes Mes Me Me  3 H Ph Mipp Mipp Me Me  4 H Ph adamantyl MesMe Me  5 H Ph DIPP DIPP Me Me  6 H Ph IPP IPP Me Me  7 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  8 H

Mes Mes Me Me  9 H

Mipp Mipp Me Me 10 H

adamantyl Mes Me Me 11 H

DIPP DIPP Me Me 12 H

IPP IPP Me Me 13 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 14 H

Mes Mes Me Me 15 H

Mipp Mipp Me Me 16 H

adamantyl Mes Me Me 17 H

DIPP DIPP Me Me 18 H

IPP IPP Me Me 19

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 20

Mes Mes Me Me 21

Mipp Mipp Me Me 22

adamantyl Mes Me Me 23

DIPP DIPP Me Me 24

IPP IPP Me Me 25 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅

26 H Ph Mes Mes

27 H Ph Mipp Mipp

28 H Ph adamantyl Mes

29 H Ph DIPP DIPP

30 H Ph IPP IPP

31 H

2-Me—C₆H₅ 2-Me—C₆H₅

32 H

Mes Mes

33 H

Mipp Mipp

34 H

adamantyl Mes

35 H

DIPP DIPP

36 H

IPP IPP

37 H

2-Me—C₆H₅ 2-Me—C₆H₅

38 H

Mes Mes

39 H

Mipp Mipp

40 H

adamantyl Mes

41 H

DIPP DIPP

42 H

IPP IPP

43

2-Me—C₆H₅ 2-Me—C₆H₅

44

Mes Mes

45

Mipp Mipp

46

adamantyl Mes

47

DIPP DIPP

48

IPP IPP

49 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 50 H Ph Mes Mes n-Bu n-Bu 51 H PhMipp Mipp n-Bu n-Bu 52 H Ph adamantyl Mes n-Bu n-Bu 53 H Ph DIPP DIPPn-Bu n-Bu 54 H Ph IPP IPP n-Bu n-Bu 55 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 56 H

Mes Mes n-Bu n-Bu 57 H

Mipp Mipp n-Bu n-Bu 58 H

adamantyl Mes n-Bu n-Bu 59 H

DIPP DIPP n-Bu n-Bu 60 H

IPP IPP n-Bu n-Bu 61 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 62 H

Mes Mes n-Bu n-Bu 63 H

Mipp Mipp n-Bu n-Bu 64 H

adamantyl Mes n-Bu n-Bu 65 H

DIPP DIPP n-Bu n-Bu 66 H

IPP IPP n-Bu n-Bu 67

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 68

Mes Mes n-Bu n-Bu 69

Mipp Mipp n-Bu n-Bu 70

adamantyl Mes n-Bu n-Bu 71

DIPP DIPP n-Bu n-Bu 72

IPP IPP n-Bu n-Buwherein: Mes is

Mipp is

DIPP is

adamantyl is

IPP is

2-Me-C₆H₅ is

Me is methyl, n-Bu is butyl [CH₃—(CH₂)₃—], Ph is phenyl, and

is [(CH₂)₄—].

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; or R^(a) and R^(b) are linked together to form a five or asix heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F;

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; or R¹ and R² are linked together to form an optionallysubstituted indenylidene;

X and Y are each N;

Q is —(CH═CH)— (i.e., a two-atom linkage having the structure—[CR¹¹═CR¹³]—; wherein R¹¹ and R¹³ are hydrogen);

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide.

Therefore, the olefin metathesis catalyst of Formula (IV), can also berepresented by the structure of Formula (VI):

wherein:

R¹ is hydrogen;

R² is unsubstituted phenyl, substituted phenyl, or substituted1-propenyl; or R¹ and R² are linked together to form an optionallysubstituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; or IV and R^(b) are linked together to form a five or a sixheterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (VI), wherein:

R¹ is hydrogen;

R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R²are linked together to form 3-phenylinden-1-ylidene;

R^(a) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, or phenyl;

R^(b) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, or phenyl;

X¹ and X² are each Cl; and

R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl; and

R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (VI), wherein:

R¹ is hydrogen;

R² is unsubstituted phenyl, substituted phenyl or substituted1-propenyl; or R¹ and R² are linked together to form an optionallysubstituted indenylidene;

R^(a) and R^(b) are linked together to form a five or a six heterocyclicmembered ring with the sulfoxide group;

X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² areeach Cl;

R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl;and

R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (VI) are described in Table (2), wherein X¹ is Cland X² is Cl.

TABLE 2 Catalyst R¹ R² R³ R⁴ R^(a) R^(b)  73 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ MeMe  74 H Ph Mes Mes Me Me  75 H Ph Mipp Mipp Me Me  76 H Ph adamantylMes Me Me  77 H Ph DIPP DIPP Me Me  78 H Ph IPP IPP Me Me  79 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  80 H

Mes Mes Me Me  81 H

Mipp Mipp Me Me  82 H

adamantyl Mes Me Me  83 H

DIPP DIPP Me Me  84 H

IPP IPP Me Me  85 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  86 H

Mes Mes Me Me  87 H

Mipp Mipp Me Me  88 H

adamantyl Mes Me Me  89 H

DIPP DIPP Me Me  90 H

IPP IPP Me Me  91

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  92

Mes Mes Me Me  93

Mipp Mipp Me Me  94

adamantyl Mes Me Me  95

DIPP DIPP Me Me  96

IPP IPP Me Me  97 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅

 98 H Ph Mes Mes

 99 H Ph Mipp Mipp

100 H Ph adamantyl Mes

101 H Ph DIPP DIPP

102 H Ph IPP IPP

103 H

2-Me—C₆H₅ 2-Me—C₆H₅

104 H

Mes Mes

105 H

Mipp Mipp

106 H

adamantyl Mes

107 H

DIPP DIPP

108 H

IPP IPP

109 H

2-Me—C₆H₅ 2-Me—C₆H₅

110 H

Mes Mes

111 H

Mipp Mipp

112 H

adamantyl Mes

113 H

DIPP DIPP

114 H

IPP IPP

115

2-Me—C₆H₅ 2-Me—C₆H₅

116

Mes Mes

117

Mipp Mipp

118

adamantyl Mes

119

DIPP DIPP

120

IPP IPP

121 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 122 H Ph Mes Mes n-Bu n-Bu 123 HPh Mipp Mipp n-Bu n-Bu 124 H Ph adamantyl Mes n-Bu n-Bu 125 H Ph DIPPDIPP n-Bu n-Bu 126 H Ph IPP IPP n-Bu n-Bu 127 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 128 H

Mes Mes n-Bu n-Bu 129 H

Mipp Mipp n-Bu n-Bu 130 H

adamantyl Mes n-Bu n-Bu 131 H

DIPP DIPP n-Bu n-Bu 132 H

IPP IPP n-Bu n-Bu 133 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 134 H

Mes Mes n-Bu n-Bu 135 H

Mipp Mipp n-Bu n-Bu 136 H

adamantyl Mes n-Bu n-Bu 137 H

DIPP DIPP n-Bu n-Bu 138 H

IPP IPP n-Bu n-Bu 139

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 140

Mes Mes n-Bu n-Bu 141

Mipp Mipp n-Bu n-Bu 142

adamantyl Mes n-Bu n-Bu 143

DIPP DIPP n-Bu n-Bu 144

IPP IPP n-Bu n-Bu

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) arelinked together to form a five or a six heterocyclic membered ring withthe sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;typically, X¹ and X² are independently Cl, Br, I, or F;

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; typically, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

Y is N;

X is CR^(3a);

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; or R^(3a) and R⁴ can form together afive to ten membered cycloalkyl or heterocyclic ring, with the carbonatom to which they are attached;

Q is a two-atom linkage having the structure—[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—; wherein R¹¹, R¹², R¹³, and R¹⁴ areindependently hydrogen, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R¹¹, R¹², R¹³,and R¹⁴ are independently hydrogen, unsubstituted C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, unsubstituted C₁-C₁₂ heteroalkyl, substitutedC₁-C₁₂ heteroalkyl, unsubstituted C₅-C₁₄ aryl, or substituted C₅-C₁₄aryl; “s” and “t” are each 1;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), (C₅-C₂₄aryl) substituted with up to three substituents selected fromunsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstitutedC₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl,substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substitutedC₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄alkaryl, and halide; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), or (C₅-C₂₄aryl) substituted with up to three substituents selected fromunsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstitutedC₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl,substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substitutedC₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄alkaryl, and halide; or R^(3a) and R⁴ can form together a five to tenmembered cycloalkyl or heterocyclic ring, with the carbon atom to whichthey are attached.

Therefore, the olefin metathesis catalyst of Formula (IV), can also berepresented by the structure of Formula (VII):

wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) arelinked together to form a five or a six heterocyclic membered ring withthe sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ arylsubstituted with up to three substituents selected from unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, or 2-methyl-phenyl;

R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R¹¹, R¹², R¹³, and R¹⁴ are independentlyhydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl,unsubstituted C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl,unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl,unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl,substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl, orsubstituted C₆-C₂₄ heteroaralkyl; typically, R¹¹ and R¹² are each methyland R¹³ and R¹⁴ are each hydrogen;

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(3a) is unsubstitutedC₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl,substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substitutedC₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl,unsubstituted C₆-C₂₄ heteroaralkyl, or substituted C₆-C₂₄ heteroaralkyl;typically, R^(3a) is methyl, ethyl, n-propyl, or phenyl; and

R⁴ is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₁-C₁₂alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl,substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substitutedC₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl,unsubstituted C₆-C₂₄ heteroaralkyl, or substituted C₆-C₂₄ heteroaralkyl;typically, R⁴ is methyl, ethyl, n-propyl, or phenyl; or R⁴ together withR^(3a) can form a five- to ten-membered cycloalkyl or heterocyclic ring,with the carbon atom to which they are attached.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (VII), wherein:

R¹ is hydrogen;

R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R²are linked together to form 3-phenylinden-1-ylidene;

R^(a) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, or phenyl;

R^(b) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, or phenyl;

X¹ and X² are each Cl; and

R³ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl, 2,6-di-ethylphenyl,2-methyl-6-tert-butylphenyl, 2-ethyl-6-methylphenyl, or 2-methyl-phenyl;

R¹¹ and R¹² are each methyl;

R¹³ and R¹⁴ are each hydrogen;

R^(3a) is methyl, ethyl, n-propyl, or phenyl; and

R⁴ is methyl, ethyl, n-propyl, or phenyl; or R^(3a) and R⁴ form togethera five-, six-, or ten-membered cycloalkyl or heterocycle ring, with thecarbon atom to which they are attached.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (VII) are described in Table (3), wherein X¹ is Cl,X² is Cl, R¹¹ is methyl, R¹² is methyl, R¹³ is hydrogen, and R¹⁴ ishydrogen.

TABLE 3 Cata- lyst R¹ R² R^(a) R^(b) R³ R^(3a) R⁴ 145 H Ph Me Me2-Me—C₆H₅ Me Me 146 H Ph Me Me Mes Me Me 147 H Ph Me Me Mipp Me Me 148 HPh Me Me EMP Me Me 149 H Ph Me Me DIPP Me Me 150 H Ph Me Me IPP Me Me151 H

Me Me 2-Me—C₆H₅ Me Me 152 H

Me Me Mes Me Me 153 H

Me Me Mipp Me Me 154 H

Me Me EMP Me Me 155 H

Me Me DIPP Me Me 156 H

Me Me IPP Me Me 157 H

Me Me 2-Me—C₆H₅ Me Me 158 H

Me Me Mes Me Me 159 H

Me Me Mipp Me Me 160 H

Me Me EMP Me Me 161 H

Me Me DIPP Me Me 162 H

Me Me IPP Me Me 163

Me Me 2-Me—C₆H₅ Me Me 164

Me Me Mes Me Me 165

Me Me Mipp Me Me 166

Me Me EMP Me Me 167

Me Me DIPP Me Me 168

Me Me IPP Me Me 169 H Ph

2-Me—C₆H₅ Me Me 170 H Ph

Mes Me Me 171 H Ph

Mipp Me Me 172 H Ph

EMP Me Me 173 H Ph

DIPP Me Me 174 H Ph

IPP Me Me 175 H

2-Me—C₆H₅ Me Me 176 H

Mes Me Me 177 H

Mipp Me Me 178 H

EMP Me Me 179 H

DIPP Me Me 180 H

IPP Me Me 181 H

2-Me—C₆H₅ Me Me 182 H

Mes Me Me 183 H

Mipp Me Me 184 H

EMP Me Me 185 H

DIPP Me Me 186 H

IPP Me Me 187

2-Me—C₆H₅ Me Me 188

Mes Me Me 189

Mipp Me Me 190

EMP Me Me 191

DIPP Me Me 192

IPP Me Me 193 H Ph n-Bu n-Bu 2-Me—C₆H₅ Me Me 194 H Ph n-Bu n-Bu Mes MeMe 195 H Ph n-Bu n-Bu Mipp Me Me 196 H Ph n-Bu n-Bu EMP Me Me 197 H Phn-Bu n-Bu DIPP Me Me 198 H Ph n-Bu n-Bu IPP Me Me 199 H

n-Bu n-Bu 2-Me—C₆H₅ Me Me 200 H

n-Bu n-Bu Mes Me Me 201 H

n-Bu n-Bu Mipp Me Me 202 H

n-Bu n-Bu EMP Me Me 203 H

n-Bu n-Bu DIPP Me Me 204 H

n-Bu n-Bu IPP Me Me 205 H

n-Bu n-Bu 2-Me—C₆H₅ Me Me 206 H

n-Bu n-Bu Mes Me Me 207 H

n-Bu n-Bu Mipp Me Me 208 H

n-Bu n-Bu EMP Me Me 209 H

n-Bu n-Bu DIPP Me Me 210 H

n-Bu n-Bu IPP Me Me 211

n-Bu n-Bu 2-Me—C₆H₅ Me Me 212

n-Bu n-Bu Mes Me Me 213

n-Bu n-Bu Mipp Me Me 214

n-Bu n-Bu EMP Me Me 215

n-Bu n-Bu DIPP Me Me 216

n-Bu n-Bu IPP Me Mewherein EMP is

In another embodiment of Formula (IV), the invention provides an olefinmetathesis catalyst wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium;typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group;

X and Y are independently C, CR^(3a), or N; and only one of X or Y canbe C or CR^(3a);

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl;

Q is a two-atom linkage having the structure—[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or [CR¹¹═CR¹³]—;

R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl;

“s” and “t” are independently 1 or 2;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹ andR² are linked together to form an optionally substituted indenylidene;

the moiety

X³ and X⁴ are independently O or S; and

R^(x), R^(y), R^(w), and R^(z) are independently hydrogen, halogen,unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; or R^(x) and R^(y) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl; or R^(w) and R^(z) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl; or R^(y) and R^(w) are linked together to form anunsubstituted bicyclic or polycyclic aryl or a substituted bicyclic orpolycyclic aryl.

In another embodiment of Formula (IV), the invention provides an olefinmetathesis catalyst wherein:

M is Ru;

n is 0;

m is 0;

R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a)is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl,or phenyl;

R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b)is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl,or phenyl; or IV and R^(b) are linked together to form a five or a sixheterocyclic membered ring with the sulfoxide group;

X and Y are each N;

Q is a two-atom linkage having the structure—[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—;

R¹¹, R¹², R¹³, and R¹⁴ are independently C₁-C₆ alkyl or hydrogen;generally, R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ ishydrogen, and R¹⁴ is hydrogen; typically, R¹¹, R¹², R¹³, and R¹⁴ areeach hydrogen;

“s” and “t” are each 1;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, orsubstituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

the moiety

X³ and X⁴ are each S; and

R^(x), R^(y), R^(w), and R^(z) are independently C₁-C₆ alkyl, hydrogen,halogen, unsubstituted phenyl, or substituted phenyl; generally, R^(x)is methyl, hydrogen, or Cl, R^(y) is hydrogen, R^(w) is hydrogen, andR^(z) is Cl, t-butyl, hydrogen, or phenyl; or R^(x) and R^(y) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl.

Therefore, the olefin metathesis catalyst of Formula (IV), can also berepresented by the structure of Formula (VIII):

wherein:

R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a)is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl,or phenyl;

R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b)is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl,or phenyl; or R^(a) and R^(b) are linked together to form a five or asix heterocyclic membered ring with the sulfoxide group;

R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to threesubstituents selected from unsubstituted C₁-C₂₀ alkyl, substitutedC₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl,unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstitutedC₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ isadamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to threesubstituents selected from unsubstituted C₁-C₂₀ alkyl, substitutedC₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl,unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstitutedC₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl, or 2-methyl-phenyl;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, orsubstituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

R¹¹, R¹², R¹³, and R¹⁴ are independently C₁-C₆ alkyl or hydrogen;generally, R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ ishydrogen, and R¹⁴ is hydrogen; typically, R¹¹, R¹², R¹³, and R¹⁴ areindependently hydrogen;

R^(x), R^(y), R^(w), and R^(z) are independently C₁-C₆ alkyl, hydrogen,halogen, unsubstituted phenyl, or substituted phenyl; generally, R^(x)is methyl, hydrogen or Cl, R^(y) is hydrogen, R^(w) is hydrogen, andR^(z) is Cl, t-butyl, hydrogen, or phenyl; or R^(x) and R^(y) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl.

In one embodiment, the invention provides an olefin metathesis catalystrepresented by the structure of Formula (VIII), wherein:

R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl,cyclohexyl, or phenyl;

R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl,cyclohexyl, or phenyl; or IV and R^(b) are linked together to form afive or a six heterocyclic membered ring with the sulfoxide group;

R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl,2,6-difluorophenyl, or 2-methyl-phenyl;

R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl,2,6-difluorophenyl, or 2-methyl-phenyl;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, orsubstituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene;

R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ is hydrogen,and R¹⁴ is hydrogen; typically, R¹¹, R¹², R¹³, and R¹⁴ are eachhydrogen;

R^(x) is methyl, hydrogen, or Cl, R^(y) is hydrogen, R^(w) is hydrogen,and R^(z) is Cl, t-butyl, hydrogen, or phenyl; or R^(x) and R^(y) arelinked together to form an unsubstituted bicyclic or polycyclic aryl ora substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linkedtogether to form an unsubstituted bicyclic or polycyclic aryl or asubstituted bicyclic or polycyclic aryl.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (VIII) are described in Table (4), wherein R^(a) ismethyl, R^(b) is methyl, R¹¹ is hydrogen, R¹² is hydrogen, R¹³ ishydrogen, R¹⁴ is hydrogen, R^(y) is hydrogen, and R^(w) is hydrogen.

TABLE 4 Catalyst R¹ R² R³ R⁴ R^(x) R^(z) 217 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ ClCl 218 H Ph Mes Mes Cl Cl 219 H Ph Mipp Mipp Cl Cl 220 H Ph DIPP DIPP ClCl 221 H Ph IPP IPP Cl Cl 222 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 223 H

Mes Mes Cl Cl 224 H

Mipp Mipp Cl Cl 225 H

DIPP DIPP Cl Cl 226 H

IPP IPP Cl Cl 227 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 228 H

Mes Mes Cl Cl 229 H

Mipp Mipp Cl Cl 230 H

DIPP DIPP Cl Cl 231 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 232 H

Mes Mes Cl Cl 233 H

Mipp Mipp Cl Cl 234 H

DIPP DIPP Cl Cl 235 H

IPP IPP Cl Cl 236 H

IPP IPP Cl Cl 237

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 238

Mes Mes Cl Cl 239

Mipp Me Cl Cl 240

DIPP DIPP Cl Cl 241

IPP Me Cl Cl 242 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 243 H Ph Mes Mes H Ph 244H Ph Mipp Mipp H Ph 245 H Ph DIPP DIPP H Ph 246 H Ph IPP IPP H Ph 247 H

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 248 H

Mes Mes H Ph 249 H

Mipp Mipp H Ph 250 H

DIPP DIPP H Ph 251 H

IPP IPP H Ph 252 H

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 253 H

Mes Mes H Ph 254 H

Mipp Mipp H Ph 255 H

DIPP DIPP H Ph 256 H

IPP IPP H Ph 257

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 258

Mes Mes H Ph 259

Mipp Mipp H Ph 260

DIPP DIPP H Ph 261

IPP IPP H Ph 262 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 263 H Ph Mes Mes Met-Bu 264 H Ph Mipp Mipp Me t-Bu 265 H Ph DIPP DIPP Me t-Bu 266 H Ph IPPIPP Me t-Bu 267 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 268 H

Mes Mes Me t-Bu 269 H

Mipp Mipp Me t-Bu 270 H

DIPP DIPP Me t-Bu 271 H

IPP IPP Me t-Bu 272 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 273 H

Mes Mes Me t-Bu 274 H

Mipp Mipp Me t-Bu 275 H

DIPP DIPP Me t-Bu 276 H

IPP IPP Me t-Bu 277

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 278

Mes Mes Me t-Bu 279

Mipp Mipp Me t-Bu 280

DIPP DIPP Me t-Bu 281

IPP IPP Me t-Bu

The present invention also concerns processes for synthesizing theolefin metathesis catalysts of the invention. The olefin metathesiscatalysts according to the invention can be prepared analogously toconventional methods as understood by the person skilled in the art ofsynthetic organic chemistry. For example, synthetic Scheme 1, set forthbelow, illustrates how the compounds according to the invention can bemade.

In a typical procedure, an olefin metathesis catalyst of general Formula(A) is reacted at room temperature with tosyl chloride (TsCl) and anexcess of sulfoxide derivative (R^(a)R^(b)SO) to produce an olefinmetathesis catalyst of general Formula (V), wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene; typically, R² is phenyl,2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linkedtogether to form 3-phenyl-1-indenylidene;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group; and

R^(j), R^(t), and R^(o) are each independently substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ aryl, substituted C₁-C₁₀ alkyl, or unsubstitutedC₁-C₁₀ alkyl; generally, R¹, R^(t), and R^(o) are each independentlyunsubstituted C₅-C₂₄ aryl; typically, R^(j), R^(t), and R^(o) are eachphenyl.

In another embodiment, the invention concerns methods of using theolefin metathesis catalysts of the invention in the synthesis of relatedolefin metathesis catalysts. The ruthenium olefin metathesis catalystsbearing sulfoxide labile ligands of the invention are excellentprecursors for various Second Generation Grubbs ruthenium olefinmetathesis catalysts. The Second Generation Grubbs ruthenium olefinmetathesis catalysts synthesized during these procedures are obtained inhigher yield and with higher purity, which presents an advantagecompared to the existing synthetic procedures.

For example, synthetic Scheme 2, set forth below, illustrates how olefinmetathesis catalysts of Formula (F) can be synthesizing from an olefinmetathesis catalyst of Formula (IV):

In a typical procedure, as shown in Scheme 2, the sulfoxide ligand ofthe olefin metathesis catalyst represented by Formula (IV) can beexchanged with “L” ligand, which is a neutral electron donor. R¹, R²,R³, R⁴, R, X¹, X², M, Q, n, m, R^(a), R^(b), and L² are as definedherein. “L” is selected from the group consisting of sulphonatedphosphine, phosphite, phosphinite, phosphonite, ether, amine, carbonyl,nitrosyl, pyridine, thioether, Grubbs-Hoveyda ligands,trimethylphosphine (PMe₃), triethylphosphine (PEt₃),tri-n-butylphosphine (PBu₃), tri(ortho-tolyl)phosphine (P-o-tolyl₃),tri-tert-butylphosphine (P-tert-Bu₃), tricyclopentylphosphine (PCp₃),tricyclohexylphosphine (PCy₃), triisopropylphosphine (P-i-Pr₃),trioctylphosphine (POct₃), triisobutylphosphine, (P-i-Bu₃),triphenylphosphine (PPh₃), tri(pentafluorophenyl)phosphine (P(C₆F₅)₃),methyldiphenylphosphine (PMePh₂), dimethylphenylphosphine (PMe₂Ph),diethylphenylphosphine (PEt₂Ph), phosphabicycloalkane (e.g.,monosubstituted 9-phosphabicyclo-[3.3.1]nonane, monosubstituted9-phosphabicyclo[4.2.1]nonane, cyclohexylphoban, isopropylphoban,ethylphoban, methylphoban, butylphoban, pentylphoban), pyridine,3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine,2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine,4-chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine,2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine,3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine,3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine,3,5-di-iso-propylpyridine, 2,4,6-trimethylpyridine,2,4,6-triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine,3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, bipyridine,pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole,pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole,3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline,bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline,naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine,quinuclidine, imidazolidine, picolylimine, purine, benzimidazole,bisimidazole, phenazine, acridine, carbazole, sulfur-containingheterocycles (e.g., thiophene, 1,2-dithiole, 1,3-dithiole, thiepine,benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene,2H-thiopyran, 4H-thiopyran, thioanthrene), oxygen-containingheterocycles (e.g. 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin,1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin, coumarone,chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene,tetrahydrofuran, 1,4-dioxan, dibenzofuran), mixed (e.g., isoxazole,oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole,1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole,3H-1,2,3-dioxazole, 3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine,2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine,phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine,benzoxazole, anthranil, and morpholine), aromatic nitrogen-containingand oxygen-containing heterocycles, monocyclic N-heteroaryl ligands thatare optionally substituted with 1 to 3, preferably 1 or 2, substituents.

The ligand exchange reactions are carried out under inert atmosphere(under nitrogen or argon). The reactions generally, are carried out atroom temperature or at temperatures from 15° C. to 25° C. or from 25° C.to 60° C., or from 35° C. to 50° C., or from 20° C. to 25° C., or from30° C. to 40° C., or from 25° C. to 45° C. The reaction times vary fromseveral minutes to several hours 12 hours, 24 hours, or 48 hours.Generally, the reactions take place in solvents such as tetrahydrofuran(THF), benzene, toluene, xylene, diethyl ether, dioxane, alcohols,methyl-tetrahydrofuran, acetone, ethyl acetate, methyl tert-butyl ether(MTBE), dimethylformamide (DMF), and dichloromethane.

In another embodiment, the invention concerns also processes forsynthesizing olefin metathesis catalysts of Formula (B) starting with anolefin metathesis catalyst of Formula (V):

In a typical procedure, as shown in Scheme 3, the sulfoxide ligand ofthe olefin metathesis catalyst represented by Formula (V) is exchangedwith a PR^(d)R^(e)OR^(f) ligand at room temperature in an inert solvent,such as dichloromethane or toluene, wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene; typically, R² is phenyl,2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linkedtogether to form 3-phenyl-1-indenylidene;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) arelinked together to form a five or a six heterocyclic membered ring withthe sulfoxide group; typically, R^(a) and R^(b) are linked together toform a tetrahydrothiophene oxide;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R^(d) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, Rd isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically, Rdis phenyl;

R^(e) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, Re isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically, Reis phenyl; and

R^(f) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R^(f) isunsubstituted C₁-C₁₀ alkyl, unsubstituted C₆-C₁₀ aryl, or unsubstitutedC₆-C₁₀ aryl; typically, R^(f) is phenyl, methyl, p-(OMe)phenyl,iso-propyl, or ethyl.

In another embodiment, the invention concerns also processes forsynthesizing olefin metathesis catalysts of Formula (C) starting with anolefin metathesis catalyst of Formula (V):

In a typical procedure, as shown in Scheme 4, the sulfoxide ligand ofthe olefin metathesis catalyst represented by Formula (V) can beexchanged with a PR^(g)OR^(h)OR^(i) ligand at room temperature in aninert solvent, such as dichloromethane or toluene, wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene; typically, R² is phenyl,2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linkedtogether to form 3-phenyl-1-indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) arelinked together to form a five or a six heterocyclic membered ring withthe sulfoxide group; typically, R^(a) and R^(b) are linked together toform a tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R^(g) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R^(g) isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically,R^(g) is phenyl;

R^(h) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R^(h) isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically,R^(h) is phenyl or methyl; and

R^(i) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R′ isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically, R′is phenyl or methyl.

In another embodiment, the invention concerns also processes forsynthesizing olefin metathesis catalysts of Formula (D) starting with anolefin metathesis catalyst of Formula (V):

In a typical procedure as shown in Scheme 5, the sulfoxide ligand of theolefin metathesis catalyst represented by Formula (V) is exchanged witha Grubbs-Hoveyda ligand at 60° C. in ethyl acetate, wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene; typically, R² is phenyl,2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linkedtogether to form 3-phenyl-1-indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linkedtogether to form a five or a six heterocyclic membered ring with thesulfoxide group; typically, IV and R^(b) are linked together to form atetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl,unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide;typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R^(k) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R^(k) ishydrogen;

R^(l) is hydrogen, halogen, —NO₂, —CN, —CF₃, SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R^(l) ishydrogen;

R^(m) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R^(m) ishydrogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅, or—NHC(O)OtBu; preferably, R^(m) is hydrogen;

R^(n) is hydrogen, halogen, —NO₂, —CN, —CF₃, SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R^(a) ishydrogen;

R^(s) is hydrogen or C₁-C₆ alkyl; typically, R^(s) is hydrogen, methyl,ethyl, or n-propyl; and

R^(q) is unsubstituted hydrocarbyl or substituted hydrocarbyl;generally, R^(q) is C₁-C₁₀ alkyl; typically, R^(q) is iso-propyl.

In another embodiment, the invention concerns also processes forsynthesizing olefin metathesis catalysts of Formula (E) starting with anolefin metathesis catalyst of Formula (V).

In a typical procedure, as shown in Scheme 6, the sulfoxide ligand ofthe olefin metathesis catalyst represented by Formula (V) can beexchanged with a P(R^(q))₃ ligand at room temperature in an inertsolvent, such as dichloromethane or toluene, wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl,or substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene; typically, R² is phenyl,2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linkedtogether to form 3-phenyl-1-indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(a) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; generally, R^(b) is unsubstitutedC₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl,n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) arelinked together to form a five or a six heterocyclic membered ring withthe sulfoxide group; typically, R^(a) and R^(b) are linked together toform a tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate;generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ arylsubstituted with up to three substituents selected from: unsubstitutedC₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substitutedC₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, andhalide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;and

R^(p) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R^(p) issubstituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; typically, R^(p) isphenyl, cyclohexyl, or cyclopentyl.

At this stage, those skilled in the art will appreciate that manyadditional compounds that fall under the scope of the invention can beprepared by performing various common chemical reactions. Details ofcertain specific chemical transformations are provided in the examples.

The metal carbene olefin metathesis catalysts can be utilized in olefinmetathesis reactions according to techniques known in the art. Forexample, the metal carbene olefin metathesis catalysts are typicallyadded to a resin composition as a solid, a solution, or as a suspension.When the metal carbene olefin metathesis catalysts are added to a resincomposition as a suspension, the metal carbene olefin metathesiscatalysts are suspended in a dispersing carrier such as mineral oil,paraffin oil, soybean oil, tri-iso-propylbenzene, or any hydrophobicliquid which has a sufficiently high viscosity so as to permit effectivedispersion of the catalyst(s), and which is sufficiently inert and whichhas a sufficiently high boiling point so that is does not act as alow-boiling impurity in the olefin metathesis reaction. It will beappreciated that the amount of catalyst that is used (i.e., the“catalyst loading”) in the reaction is dependent upon a variety offactors such as the identity of the reactants and the reactionconditions that are employed. It is therefore understood that catalystloading can be optimally and independently chosen for each reaction. Ingeneral, however, the catalyst will be present in an amount that rangesfrom a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm,15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relativeto the amount of an olefinic substrate (e.g., cyclic olefins).

Cyclic Olefins

Resin compositions that may be used with the present invention disclosedherein comprise one or more cyclic olefins. Such cyclic olefins may beoptionally substituted, optionally heteroatom-containing,mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefinmay generally be any strained or unstrained cyclic olefin, provided thecyclic olefin is able to participate in a ROMP reaction eitherindividually or as part of a ROMP cyclic olefin composition.

Examples of bicyclic and polycyclic olefins thus include, withoutlimitation, dicyclopentadiene (DCPD); trimer and other higher orderoligomers of cyclopentadiene including without limitationtricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer,and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene;norbornene; C₂-C₁₂ hydrocarbyl substituted norbornenes;5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene;5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene;5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene;5-propenyl-2-norbornene; 5-butenyl-2-norbornene; 5-tolyl-norbornene;5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene;5,6-dimethyl-2-norbornene; 5-phenyl norbornene; 5-benzylnorbornene;5-acetylnorbornene; 5-methoxycarbonylnorbornene;5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene;bicyclo[2.2.1]hept-2-ene-2-carboxylic acid, 2-ethylhexyl ester;5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene;cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene;2,3-dimethoxynorbornene; norbornadiene; tricycloundecene;tetracyclododecene; 8-methyl tetracyclododecene;8-ethyltetracyclododecene; 8-methoxy carbonyltetracyclo dodecene;8-methyl-8-tetra cyclododecene; 8-cyanotetracyclo dodecene;pentacyclopentadecene; pentacyclo hexadecene;bicyclo[2.2.1]hept-2-ene-5-phenoxymethyl; 2-ethylhexylester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; 2-hydroxyethylester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid;bicyclo[2.2.1]hept-5-ene-2-methanol;bicyclo[2.2.1]hept-5-ene-2-heptanoic acid-methyl ester;bicyclo[2.2.1]hept-5-ene-2-hexanoic acid-methyl ester;1,4:5,8-dimethanonaphthalene, 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro;bicyclo[2.2.1]hept-5-ene-2-octanoic acid-methyl ester; 1,4:5,8-dimethanonaphthalene; 2-butyl-1,2,3,4,4a,5,8,8a-octahydro;ethylidenetetracyclododecene;2-vinyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethano naphthalene; andthe like, and their structural isomers, stereoisomers, and mixturesthereof.

EXPERIMENTAL General Information—Materials and Methods

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g., amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. The examplesare to be considered as not being limiting of the invention describedherein. Surprisingly, the olefin metathesis catalysts of the inventionwere obtained only in the cis configuration, no traces of the transstereoisomers were detected.

All reactions involving metal complexes were conducted in oven-driedglassware under an argon or nitrogen atmosphere using standard Schlenktechniques. Chemicals and solvents were obtained from Sigma-Aldrich,Strem, Alfa Aesar, Nexeo, Brenntag, A G Layne and TCI. Commerciallyavailable reagents were used as received unless otherwise noted. Silicagel was purchased from Fisher (0.040-0.063 μm, EMD Millipore).

The crystallographic measurements were performed at 100(2) K using aBruker APEXII CCD area detector diffractometer (Mo-K_(α) radiation,λ=0.71073 Å). In each case, a specimen of suitable size and quality wasselected and mounted onto a nylon loop. The structures were solved bydirect methods, which successfully located most of the non-hydrogenatoms. Semi-empirical absorption corrections were applied. Subsequentrefinement on F² using the SHELXTL/PC package (version 6.1) allowedlocation of the remaining non-hydrogen atoms.

Ultrene® 99 dicyclopentadiene (DCPD) was obtained from CymetechCorporation. A modified DCPD base resin containing 20-25%tricyclopentadiene (and small amounts of higher cyclopentadienehomologs) (DCPD-HT) was prepared by heat treatment of Ultrene® 99 DCPDgenerally as described in U.S. Pat. No. 4,899,005.

Catalysts C931, C933, C793, C827, C705, C727, C748, and C848 wereprepared using known methods.

¹H and ¹³C NMR spectra were recorded on a Varian 400 MHz spectrometer.Chemical shifts are reported in ppm downfield from Me₄Si by using theresidual solvent peak as an internal standard (CDCl₃δ 7.24 ppm). Spectrawere analyzed and processed using MestReNova software.

General GC method conditions: injection temperature, 250° C.; detectortemperature, 280° C.; oven temperature, starting temperature, 100° C.;hold time, 1 min. The ramp rate was 10° C./min to 250° C., hold time 12min; carrier gas helium.

GC Method 1: Column: DB-225, 30 m×0.25 mm (ID)×0.25 μm film thickness.Manufacturer: Agilent; GC and column conditions: Injector temperature:220° C., Detector temperature: 220° C.; Oven temperature: Startingtemperature: 35° C., hold time: 0.5 minutes.

Ramp rate 10° C./min to 130° C., hold time: 0 minutes. Ramp rate 20°C./min to 220° C., hold time: 5 minutes. Carrier gas: Helium. Mean gasvelocity: 25 cm/sec. Split ratio: 20:1.

The following abbreviations are used in the examples:

mL milliliterDCM/CH₂Cl₂ dichloromethaneC₆D₆ deuterated benzeneCDCl₃ deuterated chloroformCD₂Cl₂ deuterated dichloromethane

C931

-   [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro    (phenylindenylidene) (triphenylphosphine)ruthenium(II)-   [CAS 340810-50-6]

C793

-   [1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)    (tricyclohexylphosphine)ruthenium(II)-   [CAS 927429-60-5]

C827

-   Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)    (tricyclohexylphosphine)ruthenium(II)-   [CAS 253688-91-4]

C933

-   Dichloro[1,3-bis(2,6-di-iso-propylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)    ruthenium(II)-   [CAS 373640-75-6]

C848

-   Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)    ruthenium(II)-   [CAS 246047-72-3]

C748

-   [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium    (II)-   [CAS 1031262-76-6]

C727

-   Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(dipyridine)    ruthenium(II)-   [CAS 357186-58-4]

C705

-   Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)(dipyridine)ruthenium(II)-   [CAS 507274-22-8]    DMSO dimethylsulfoxide    PCy₃ tricyclohexylphosphine    EtOAc ethylacetate    MTBE methyl tert-butyl ether    THF tetrahydrofuran    CHP cumene hydroperoxide    5C14 5-tetradecene    5C10 5-decene    9C18 9-octadecene

EXAMPLES Example 1 Synthesis of C747

To a 20 mL scintillation vial equipped with a magnetic stir bar wereadded C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g,0.268 mmol), dimethyl sulfoxide (0.210 g, 2.68 mmol), anddichloromethane (4 mL). The reaction was stirred for one hour thenfiltered through a plug of celite and combined with diethyl ether (30mL). The resulting black precipitate was isolated by filtration, washedwith diethyl ether (2×10 mL) then dried in vacuum to afford C747 as ablack powder (0.346 g, 86.3% yield). The X-ray structure of C747 isshown in FIG. 1.

¹H NMR (400 MHz, CDCl₃): δ 8.68 (d, J=7.4 Hz, 1H), 7.71 (d, J=7.6 Hz,2H), 7.52 (t, J=7.1 Hz, 1H), 7.42 (t, J=7.5 Hz, 2H), 7.31 (t, J=7.4 Hz,1H), 7.25 (t, J=7.1 Hz, 1H), 7.11 (d, J=6.1 Hz, 2H), 7.04 (d, J=7.0 Hz,1H), 6.86 (s, 1H), 6.26 (d, J=3.8 Hz, 2H), 4.13-3.99 (m, 1H), 3.99-3.80(m, 2H), 3.80-3.69 (m, 1H), 2.82 (s, 3H), 2.69 (s, 3H), 2.68 (s, 3H),2.41 (s, 3H), 2.35 (s, 3H), 2.11 (s, 3H), 2.05 (s, 3H), 1.77 (s, 3H).

Example 2 Synthesis of C647_(m)

To a 40 mL scintillation vial equipped with a magnetic stir bar wereadded C848 (0.500 g, 0.589 mmol), p-toluenesulfonyl chloride (0.056 g,0.30 mmol), dimethyl sulfoxide (0.230 g, 2.94 mmol), and dichloromethane(4 mL). The reaction was stirred at ambient temperature for one hourthen filtered through a plug of celite and combined with diethyl ether(30 mL). The resulting purple precipitate was isolated by filtration,washed with diethyl ether (2×10 mL) then dried in vacuum to affordC647_(m) as a purple crystalline solid (0.269 g, 70.7% yield). The X-raystructure of C647_(m) is shown in FIG. 2.

¹H NMR (400 MHz, C₆D₆) δ 16.03 (s, 1H), 8.15 (d, J=25.0 Hz, 2H), 7.21(t, J=7.3 Hz, 1H), 7.00 (t, J=7.8 Hz, 2H), 6.84 (s, 1H), 6.75 (s, 1H),6.65 (s, 1H), 6.17 (s, 1H), 3.33-3.00 (m, 4H), 2.87 (s, 3H), 2.67 (s,3H), 2.61 (s, 3H), 2.22 (s, 3H), 2.14 (s, 3H), 2.07 (s, 3H), 2.04 (s,3H), 1.98 (s, 3H).

Example 3 Synthesis of C731

To a 40 mL scintillation vial equipped with a magnetic stir bar wereadded C933 (0.500 g, 0.536 mmol), p-toluenesulfonyl chloride (0.051 g,0.27 mmol), dimethyl sulfoxide (0.209 g, 2.68 mmol), and ethyl acetate(10 mL). The reaction was stirred at ambient temperature for three hoursaffording a fine blue-gray precipitate. The solid was isolated byfiltration, washed with ethyl acetate (2×5 mL) then dried in vacuum toafford C731 as a blue-gray solid (0.148 g, 37.8% yield).

¹H NMR (400 MHz, C₆D₆): δ 16.16 (s, 1H), 7.99 (s, 2H), 7.31-7.01 (m,6H), 6.94 (t, J=7.2 Hz, 2H), 6.65 (d, J=7.2 Hz, 1H), 4.63-4.48 (m, 1H),4.07-3.92 (m, 1H), 3.76-3.60 (m, 2H), 3.60-3.44 (m, 3H), 3.42-3.27 (m,1H), 1.97 (s, 3H), 1.87 (d, J=6.0 Hz, 3H), 1.72 (s, 3H), 1.67 (d, J=6.7Hz, 3H), 1.65 (d, J=6.8 Hz, 3H), 1.20 (d, J=6.3 Hz, 3H), 1.12 (d, J=6.3Hz, 3H), 1.04 (d, J=6.1 Hz, 3H), 0.88 (d, J=6.5 Hz, 3H), 0.77 (d, J=5.7Hz, 3H).

Example 4 Synthesis of C591

To a 40 mL scintillation vial equipped with a magnetic stir bar wereadded C793 (0.500 g, 0.631 mmol), p-toluenesulfonyl chloride (0.060 g,0.32 mmol), dimethyl sulfoxide (0.246 g, 3.15 mmol), and methyltert-butyl ether (10 mL). The reaction was stirred at ambienttemperature for four hours affording a purple precipitate. The solid wasisolated by filtration then recrystallized from dichloromethane anddiethyl ether. The resulting purple crystals were isolated byfiltration, washed with diethyl ether (2×5 mL) then dried in vacuum toafford C591 as a purple crystalline solid (0.234 g, 62.7% yield). Twoisomers [87:13], which are not stereoisomers, were observed in solution.

¹H NMR (400 MHz, CD₂Cl₂, major isomer) δ 15.82 (s, 1H), 8.72 (d, J=7.7Hz, 1H), 7.78 (d, J=7.5 Hz, 2H), 7.56 (dd, J=16.6, 8.1 Hz, 2H),7.52-7.39 (m, 2H), 7.24 (t, J=7.9 Hz, 3H), 7.15 (d, J=7.9 Hz, 1H), 6.96(t, J=7.5 Hz, 1H), 6.45 (t, J=7.6 Hz, 1H), 4.59-4.47 (m, 1H), 4.22 (q,J=10.1 Hz, 1H), 3.90 (q, J=10.4 Hz, 1H), 3.83-3.72 (m, 1H), 2.67 (s,3H), 2.59 (s, 3H), 2.29 (s, 3H), 1.90 (s, 3H).

¹H NMR (400 MHz, CD₂Cl₂, minor isomer, selected resonances) δ 16.02 (s,1H), 8.91 (d, J=7.7 Hz, 1H), 7.73 (d, J=7.6 Hz, 3H), 6.90-6.84 (m, 1H),4.43-4.34 (m, 1H), 2.40 (s, 3H), 2.01 (s, 3H), 1.96 (s, 3H).

Example 5 Synthesis of C625

To a 40 mL scintillation vial equipped with a magnetic stir bar wereadded C827 (0.500 g, 0.605 mmol), p-toluenesulfonyl chloride (0.058 g,0.30 mmol), dimethyl sulfoxide (0.236 g, 3.02 mmol), and methyltert-butyl ether (10 mL). The reaction was stirred at ambienttemperature for twenty four hours and the resulting brown precipitatewas isolated by filtration, washed with methyl tert-butyl ether (2×10mL) then dried in vacuum to afford C625 as a light brown solid (0.298 g,78.8% yield).

¹H NMR (400 MHz, CDCl₃) δ 16.10 (d, J=11.3 Hz, 1H), 7.83 (d, J=11.2 Hz,1H), 7.08 (s, 1H), 7.05 (s, 1H), 6.82 (s, 1H), 6.73 (s, 1H), 4.13-4.00(m, 1H), 4.00-3.78 (m, 3H), 2.73 (s, 6H), 2.55 (s, 3H), 2.54 (s, 3H),2.38 (s, 3H), 2.32 (s, 3H), 2.22 (s, 6H), 1.33 (s, 3H), 1.27 (s, 3H).

Example 6 Synthesis of C865

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g,0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2.68 mmol), andtoluene (5 mL). The reaction was stirred at ambient temperature for twohours then diluted with diethyl ether (15 mL). The precipitate wasisolated by filtration, washed with diethyl ether (2×20 mL) followed byhexanes (1×20 mL) then dried in vacuum to afford C865 (0.418 g, 90.0%yield).

¹H NMR (400 MHz, CDCl₃) δ 8.72 (d, J=7.2 Hz, 1H), 7.71 (d, J=7.7 Hz,2H), 7.52 (t, J=7.3 Hz, 1H), 7.42 (t, J=7.5 Hz, 2H), 7.33-7.20 (m, 4H),7.20-7.14 (m, 3H), 7.11 (d, J=8.9 Hz, 2H), 7.04 (d, J=7.0 Hz, 1H), 6.93(s, 1H), 6.28 (s, 2H), 4.15-4.03 (m, 1H), 4.03-3.86 (m, 2H), 3.84-3.71(m, 1H), 2.92-2.85 (m, 2H), 2.84 (s, 3H), 2.69 (s, 3H), 2.70-2.60 (m,1H), 2.43 (s, 3H), 2.36 (s, 3H), 2.35 (s, 3H), 2.09 (s, 3H), 2.15-2.04(m, 1H), 2.04-1.90 (m, 2H), 1.78 (s, 3H), 1.82-1.73 (m, 2H).

Example 7 Synthesis of C861

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g,0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2.68 mmol), and ethylacetate (5 mL). The reaction was stirred at ambient temperature forthree hours then diluted with diethyl ether (25 mL). The precipitate wasisolated by filtration, washed with diethyl ether (2×10 mL) followed byhexanes (1×20 mL) then dried in vacuum to afford C861 (0.386 g, 83.5%yield).

¹H NMR (400 MHz, CDCl₃) δ 8.71 (d, J=7.2 Hz, 1H), 7.70 (d, J=7.7 Hz,2H), 7.51 (t, J=7.2 Hz, 1H), 7.41 (t, J=7.4 Hz, 2H), 7.33-7.19 (m, 2H),7.11 (d, J=8.1 Hz, 2H), 7.03 (d, J=7.1 Hz, 1H), 6.92 (s, 1H), 6.27 (s,2H), 4.11 (dd, J=14.3, 7.1 Hz, 2H), 4.15-4.02 (m, 1H), 4.03-3.85 (m,2H), 3.84-3.71 (m, 1H), 2.92-2.79 (m, 2H), 2.83 (s, 3H), 2.68 (s, 3H),2.70-2.59 (m, 1H), 2.42 (s, 3H), 2.35 (s, 3H), 2.08 (s, 3H), 2.15-2.07(m, 1H), 2.03 (s, 3H), 2.02-1.90 (m, 2H), 1.77 (s, 3H), 1.82-1.73 (m,2H), 1.25 (t, J=7.1 Hz, 3H).

Example 8 Synthesis of C773

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g,0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2.68 mmol), anddichloromethane (4 mL). The reaction was stirred at ambient temperaturefor three hours then diluted with diethyl ether (30 mL). The precipitatewas isolated by filtration, washed with diethyl ether (2×10 mL) followedby hexanes (1×20 mL) then dried in vacuum to afford C773 (0.345 g, 83.0%yield).

¹H NMR (400 MHz, CDCl₃) δ 8.71 (d, J=7.1 Hz, 1H), 7.71 (d, J=7.6 Hz,2H), 7.52 (t, J=7.1 Hz, 1H), 7.42 (t, J=7.4 Hz, 2H), 7.34-7.19 (m, 2H),7.11 (d, J=8.0 Hz, 2H), 7.03 (d, J=7.0 Hz, 1H), 6.92 (s, 1H), 6.28 (s,2H), 4.14-4.03 (m, 1H), 4.03-3.86 (m, 2H), 3.82-3.72 (m, 1H), 2.83 (s,3H), 2.91-2.79 (m, 2H), 2.69 (s, 3H), 2.72-2.60 (m, 1H), 2.42 (s, 3H),2.36 (s, 3H), 2.18-2.04 (m, 1H), 2.08 (s, 3H). 2.04-1.88 (m, 2H), 1.77(s, 3H), 1.82-1.73 (m, 2H).

Example 9 Synthesis of C673

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C848 (0.500 g, 0.589 mmol), p-toluenesulfonyl chloride (0.056 g,0.30 mmol), tetrahydrothiophene 1-oxide (0.307 g, 2.94 mmol), anddichloromethane (4 mL). The reaction was stirred at ambient temperaturefor one hour then diluted with diethyl ether (25 mL). The precipitatewas isolated by filtration, washed with diethyl ether (2×10 mL) followedby hexanes (1×15 mL) then dried in vacuum to afford C673 (0.248 g, 62.6%yield).

¹H NMR (400 MHz, CDCl₃) δ 16.12 (s, 1H), 7.82 (d, J=7.7 Hz, 2H), 7.55(t, J=7.2 Hz, 1H), 7.23 (t, J=7.7 Hz, 2H), 7.11 (br s, 2H), 6.93 (s,1H), 6.29 (s, 1H), 4.11-3.94 (m, 3H), 3.86-3.76 (m, 1H), 2.72 (s, 3H),2.69 (s, 3H), 2.64 (s, 3H), 2.62-2.45 (m, 3H), 2.35 (s, 3H), 2.27-2.17(m, 1H), 2.15 (s, 3H), 2.07 (s, 3H), 2.05-1.91 (m, 2H), 1.84-1.68 (m,2H).

Example 10 Synthesis of C651

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C827 (0.500 g, 0.605 mmol), p-toluenesulfonyl chloride (0.058 g,0.30 mmol), tetrahydrothiophene 1-oxide (0.315 g, 3.02 mmol), and ethylacetate (5 mL). The reaction was stirred at ambient temperature for 16hours. The precipitate was isolated by filtration and recrystallizedfrom dichloromethane/methanol at −30° C. The resulting purplecrystalline product was isolated by filtration, washed withdichloromethane/methanol (1:10, 2×5 mL) then dried in vacuum to affordC651 (0.141 g, 35.7% yield).

¹H NMR (400 MHz, CDCl₃) δ 16.73 (d, J=11.3 Hz, 1H), 7.66 (d, J=11.5 Hz,1H), 7.09 (s, 1H), 7.05 (s, 1H), 6.83 (s, 1H), 6.71 (s, 1H), 4.17-4.02(m, 1H), 4.01-3.84 (m, 3H), 3.16-3.06 (m, 1H), 3.02-2.89 (m, 1H),2.85-2.74 (m, 2H), 2.75 (s, 3H), 2.59 (s, 3H), 2.54 (s, 3H), 2.33 (s,6H), 2.22 (s, 3H), 2.14-2.02 (m, 2H), 1.99-1.83 (m, 2H), 1.34 (s, 3H),1.26 (s, 3H).

Example 11 Synthesis of C831_(m)

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g,0.27 mmol), dibutyl sulfoxide (0.436 g, 2.69 mmol), and diethyl ether(10 mL). The reaction was stirred at ambient temperature for twelvehours. The precipitate was isolated by filtration, washed with diethylether (1×10 mL) followed by hexanes (1×20 mL) then dried in vacuum toafford C831_(m) (0.195 g, 43.7% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 8.68-8.60 (m, 1H), 7.77-7.69 (m, 2H),7.57-7.50 (m, 1H), 7.44 (t, J=7.5 Hz, 2H), 7.35-7.28 (m, 2H), 7.15 (s,1H), 7.13 (dd, J=5.6, 2.7 Hz, 1H), 7.07 (s, 1H), 6.77 (s, 1H), 6.36 (s,1H), 6.21 (s, 1H), 4.06-3.95 (m, 1H), 3.94-3.81 (m, 2H), 3.78-3.65 (m,1H), 2.94 (ddd, J=14.5, 12.3, 5.6 Hz, 1H), 2.77 (s, 3H), 2.70 (s, 3H),2.64-2.51 (m, 1H), 2.47 (s, 3H), 2.36 (s, 3H), 1.95 (s, 3H), 1.73 (s,3H), 1.71-1.60 (m, 1H), 1.60-1.43 (m, 2H), 1.33-1.19 (m, 2H), 1.19-1.03(m, 2H), 0.98-0.91 (m, 2H), 0.88 (t, J=7.2 Hz, 3H), 0.83-0.70 (m, 1H),0.48 (t, J=7.3 Hz, 3H).

Example 12 Synthesis of C885_(ss)

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C747 (0.590 g, 0.790 mmol),(3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.291 g,0.869 mmol), and tetrahydrofuran (8 mL). The reaction was stirred atambient temperature for one hour then concentrated to dryness. Theresulting residue was extracted with dichloromethane (10 mL), filteredthrough a plug of celite, and then concentrated in vacuum to about 5 mL.Slow addition of hexanes (30 mL) with rapid stirring afforded aprecipitate that was isolated by filtration, washed with hexanes (2×10mL) then dried in vacuum to afford C885_(ss ()0.604 g, 86.4% yield) as adark purple powder.

¹H NMR (400 MHz, CD₂Cl₂) δ 7.76 (d, J=7.3 Hz, 2H), 7.55-7.40 (m, 3H),7.31 (br s, 1H), 7.20 (br s, 1H), 7.12 (br s, 1H), 7.04 (t, J=7.3 Hz,2H), 6.97 (d, J=6.7 Hz, 1H), 6.84 (br s, 1H), 6.74 (t, J=7.2 Hz, 1H),6.31 (d, J=7.6 Hz, 2H), 6.19 (br s, 1H), 4.03 (br s, 1H), 3.92 (br s,3H), 2.90 (br s, 3H), 2.64 (br s, 3H), 2.43 (br s, 6H), 2.26 (br s, 6H),2.18 (br s, 3H), 1.78 (br s, 3H).

Example 13 Synthesis of C785_(ss)

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C647 (0.300 g, 0.464 mmol),(3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine) zinc(II) (0.171 g,0.510 mmol), and tetrahydrofuran (5 mL). The reaction was stirred atambient temperature for thirty minutes then concentrated to dryness. Theresulting residue was extracted with dichloromethane (20 mL), passedthrough a 0.2 μm syringe filter, and then concentrated in vacuum to ca.4 mL. Diethyl ether (30 mL) was added slowly affording a greenmicrocrystalline precipitate. The product was isolated by filtration,washed with diethyl ether (2×5 mL) and dried in vacuum to affordC785_(ss) (0.283 g, 77.8% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 14.77 (s, 1H), 7.28 (t, J=7.3 Hz, 1H), 7.18(d, J=8.1 Hz, 1H), 7.10 (d, J=8.2 Hz, 1H), 7.06 (s, 1H), 6.90-6.81 (m,4H), 6.47 (d, J=7.3 Hz, 2H), 6.23 (s, 1H), 4.10-3.90 (m, 4H), 2.71 (s,3H), 2.68 (s, 3H), 2.66 (s, 3H), 2.35 (s, 3H), 2.30 (s, 3H), 2.28 (s,3H), 2.21 (s, 3H), 2.02 (s, 3H).

Synthesis of Second Generation Grubbs Ruthenium Olefin MetathesisCatalysts Example 14 Synthesis of C947 from C747

To a 20 mL scintillation vial equipped with a magnetic stir bar wereadded C747 (0.500 g, 0.670 mmol), (PhO)PPh₂ ([CAS 13360-92-4] 0.196 g,0.703 mmol), and dichloromethane (5 mL). The reaction was stirred atambient temperature for one hour then concentrated to 1 mL under vacuum.Hexanes (14 mL) was added and the resulting precipitate was isolated byfiltration, washed with hexanes (2×10 mL) then dried in vacuum to affordC947 as a red-brown powder (0.599 g, 94.5% yield). The ¹H NMR datacorrespond to the data found in the literature.

Example 15 Synthesis of C627 from C747

To a 20 mL scintillation vial equipped with a magnetic stir bar wereadded C747 (0.500 g, 0.670 mmol), 2-isopropoxy-β-methylstyrene (0.153 g,0.870 mmol), heptanes (5 mL), and methanol (1 mL). The reaction wasstirred at 60° C. for two hours then cooled to ambient temperature. Theresulting precipitate was isolated by filtration, washed with methanol(2×5 mL) then dried in vacuum to afford C627 as a green solid (0.332 g,79.1% yield). The ¹H NMR data correspond to the data found in theliterature.

Example 16 Synthesis of C627 from C647_(m)

To a 20 mL scintillation vial equipped with a magnetic stir bar wereadded C647m (0.400 g, 0.619 mmol), 2-isopropoxy-P-methylstyrene (0.142g, 0.804 mmol), heptanes (5 mL), and methanol (1 mL). The reaction wasstirred at 60° C. for one hour then cooled to ambient temperature. Theresulting precipitate was isolated by filtration, washed with methanol(2×5 mL) then dried in vacuum to afford C627 as a green solid (0.228 g,58.9% yield). The ¹H NMR data correspond to the data found in theliterature.

Example 17 Synthesis of C848 from C747

To a 20 mL scintillation vial was added C747 (0.300 g, 0.402 mmol),internal olefin [stilbene or β-methylstyrene] (3.6-10 equiv), andhalogenated solvent (chloroform or dichloromethane, 4 mL). Reactionswere heated at 40 or 60° C. with stirring until <5% C747 remained asdetermined by ¹H NMR spectroscopy (2 to 24 hours). PCy₃ (0.124 g, 0.442mmol) was subsequently added and the reaction stirred for an additional30 minutes. Yields of C848 ranged from 50-80% as judged by ¹H and ³¹PNMR spectroscopy. The ¹H NMR data correspond to the data found in theliterature.

Catalytic Activity of the Olefin Metathesis Catalysts of the InventionExample 18 ROMP Reaction of DCPD-HT

The catalytic activity of the complexes according to the invention wasevaluated in ROMP reactions as follows. A 250 mL beaker was filled with100 g of DCPD-HT monomer and 50 ppm of CHP. The monomer was equilibratedto the desired temperature in an oil bath (30° C.+/−0.5° C.). A J-Typethermocouple was suspended directly into the center of the monomer. Thecatalyst under study was dissolved in solvent (either toluene or CH₂Cl₂)to form a catalyst solution and the catalyst solution was then added tothe monomer at a molar ratio of 45,000:1 (monomer:catalyst) to form aROMP composition. Addition of the catalyst to the monomer to form theROMP composition denoted the start of the ROMP reaction and hence, thiswas time point zero. Temperature readings were recorded using thethermocouple. The exotherm time was determined by measuring the amountof time that passed (i.e., the time difference) between time point zeroand the time point that a propagating interface of the ROMP compositionwas first visually observed as the ROMP composition transitioned from aliquid state or gel state to a cured polymer state. ROMP reactions werestopped 2 hours after addition of the catalyst solution to the monomer.Time to exotherm is expressed by: slow>120 minutes; moderate 30-120minutes; medium 1-<30 minutes; fast<1 minute and peak exothermtemperature. The results are shown in Table (5).

TABLE (5) DCPD-HT Monomer Peak Exotherm Catalyst Temperature (° C.)Temperature (° C.) Time to Exotherm C647_(m) 30 186 medium C861 30 190medium C865 30 188 medium C773 30 188 medium C673 30 188 medium C625 30190 fast C651 30 192 moderate C731 30 171 slow C591 30 167 moderate

Example 19 RCM of Diethyl-2,2-diallylmalonate

Following the procedure outlined in Organometallics, 2006, 25,5740-5745, inside an argon filled glovebox, a screwcap NMR tube fittedwith a PTFE septum was charged with CD₂C₁₂ (0.75 mL or 0.775 mL) andcatalyst stock solution (0.016 M, 50 μL, 0.80 μmol, 1.0 mol % or 0.016M, 25 μL, 0.80 μmol, 0.5 mol %). Samples were equilibrated to 30° C. ina preheated NMR probe before diethyl 2,2-diallylmalonate (19.3 μL, 19.2mg, 0.080 mmol, 0.1 M) was added via syringe. The ensuing reaction wasmonitored for 30 minutes using the Varian array function and theconversion to diethyl cyclopent-3-ene-1,1-dicarboxylate was determinedby comparing the ratio of the integrals of the methylene protons in thestarting material, δ 2.61 (dt), with those in the product, δ 2.98 (s).FIG. 3 shows the conversion of diethyl 2,2-diallylmalonate to4,4-bis(ethoxy carbonyl)cyclopentene, wherein Catalyst is: C747, C748,C647, C773, C625, C727, or C705.

Example 20 Self-Metathesis of cis-5-Tetradecene (5C14)

In an argon filled glovebox, a 4 mL scintillation vial equipped with amagnetic stir bar was charged with C785ss (0.0046 g, 0.0059 mmol) andtetrahydrofuran (0.5 mL). cis-5-Tetradecene (0.150 mL total, 0.588 mmol)was subsequently added, the vial was sealed and stirred at 40° C. Thereaction was sampled at appropriate time intervals andyields/stereoselectivies were determined by gas chromatography(Method 1) as shown in Table (6).

TABLE (6) 5C14 5C10 9C18 9C18 time (h) yield (%) yield (%) yield (%)(Z/E) 1 50 24 25 93/7 2 50 24 24 92/8

1.-20. (canceled)
 21. An olefin metathesis catalyst represented by thestructure of Formula (IV):

wherein: M is a Group 8 transition metal; L² is a neutral electron donorligand; n is 0 or 1; m is 0, 1 or 2; R^(a) is hydrogen, unsubstitutedhydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; R^(b) is hydrogen, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; or R^(a) and R^(b) arelinked together to form a five or a six heterocyclic membered ring withthe sulfoxide group; X¹ and X² are independently anionic ligands; R¹ andR² are independently hydrogen, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; or R¹ and R² are linkedtogether to form an optionally substituted indenylidene; X and Y areindependently C, CR3a or N; and only one of X or Y can be C or CR3a;R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; Q is a two-atom linkage having thestructure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or —[CR¹¹═CR¹³]—; R¹¹, R¹², R¹³,and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl; “s” and“t” are independently 1 or 2; R³ is unsubstituted hydrocarbyl,substituted hydrocarbyl, unsubstituted heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl; and R⁴ isunsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl.
 22. The olefin metathesis catalyst according to claim 21,wherein: M is Ru; n is 0; m is 0; R^(a) is unsubstituted C₁-C₁₀ alkyl,substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substitutedC₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl;R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; or R^(a) and R^(b)are linked together to form a five or a six heterocyclic membered ringwith the sulfoxide group; X¹ and X² are independently halogen; R¹ ishydrogen; R² is unsubstituted phenyl, substituted phenyl or substituted1-propenyl; or R¹ and R² are linked together to form an optionallysubstituted indenylidene; X and Y are independently N; Q is a two-atomlinkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—; R¹¹, R¹²,R¹³, and R¹⁴ are independently hydrogen; “s” and “t” are independently1; R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to threesubstituents selected from: unsubstituted C₁-C₂₀ alkyl, substitutedC₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl,unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstitutedC₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; and R⁴ isunsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to threesubstituents selected from: unsubstituted C₁-C₂₀ alkyl, substitutedC₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl,unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstitutedC₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide.
 23. The olefinmetathesis catalyst according to claim 22, represented by the structureof Formula (V),

wherein: R¹ is hydrogen; R² is unsubstituted phenyl, substituted phenylor substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene; R^(a) is methyl, ethyl, n-propyl,iso-propyl, n-butyl, tert-butyl, or phenyl; R^(b) is methyl, ethyl,n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; or R^(a) and R^(b)are linked together to form a tetrahydrothiophene oxide with thesulfoxide group; X¹ and X² are independently Cl, Br, F or I; R³ isadamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl; andR⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl. 24.The olefin metathesis catalyst according to claim 23, wherein: R² isphenyl or 2-methyl-1-propenyl; or R¹ and R² are linked together to form3-phenylinden-1-ylidene; and X¹ and X² are independently Cl.
 25. Theolefin metathesis catalyst according to claim 24, wherein: R^(a) ismethyl; R^(b) is methyl; R³ is 2,4,6-trimethylphenyl; and R⁴ is2,4,6-trimethylphenyl.
 26. The olefin metathesis catalyst according toclaim 25, wherein: R¹ and R² are linked together to form3-phenylinden-1-ylidene.
 27. The olefin metathesis catalyst according toclaim 23, wherein: R^(a) and R^(b) form a tetrahydrothiophene oxide; andX¹ and X² are independently Cl.
 28. The olefin metathesis catalystaccording to claim 27, wherein: R² is phenyl or 2-methyl-1-propenyl; R³is 2,4,6-trimethylphenyl; and R⁴ is 2,4,6-trimethylphenyl.
 29. Theolefin metathesis catalyst according to claim 27, wherein: R¹ and R² arelinked together to form 3-phenylinden-1-ylidene; R³ is2,4,6-trimethylphenyl; and R⁴ is 2,4,6-trimethylphenyl.
 30. The olefinmetathesis catalyst according to claim 23, selected from:


31. The olefin metathesis catalyst according to claim 21, wherein: M isRu; n is 0; m is 0; R^(a) is unsubstituted C₁-C₁₀ alkyl, substitutedC₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; R^(b)is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstitutedC₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄aryl or substituted C₅-C₂₄ aryl; or R^(a) and R^(b) are linked togetherto form a five or a six heterocyclic membered ring with the sulfoxidegroup; X¹ and X² are independently halogen; R¹ is hydrogen; R² isunsubstituted phenyl, substituted phenyl or substituted 1-propenyl; orR¹ and R² are linked together to form an optionally substitutedindenylidene; X is CR^(3a); Y is N; Q is a two-atom linkage having thestructure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—; R¹¹, R¹², R¹³, and R¹⁴ areindependently hydrogen, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; “s” and “t” areindependently 1; R³ is unsubstituted C₃-C₁₀ cycloalkyl, substitutedC₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substitutedwith up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl,substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substitutedC₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl,unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstitutedC₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; and R⁴ isunsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to threesubstituents selected from: unsubstituted C₁-C₂₀ alkyl, substitutedC₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl,unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl,unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstitutedC₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide.
 32. The olefinmetathesis catalyst according to claim 31, represented by the structureof Formula (VII)

wherein: R¹ is hydrogen; R² is unsubstituted phenyl, substituted phenylor substituted 1-propenyl; or R¹ and R² are linked together to form anoptionally substituted indenylidene; R^(a) is methyl, ethyl, n-propyl,iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; R^(b) is methyl,ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;or R^(a) and R^(b) are linked together to form a five or a sixheterocyclic membered ring with the sulfoxide group; X¹ and X² areindependently Cl, Br, I or F; R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl or 2-methyl-phenyl; R¹¹, R¹², R¹³ and R¹⁴ areindependently hydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂alkyl, unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl,unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl,substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl orsubstituted C₆-C₂₄ heteroaralkyl; R^(3a) is methyl, ethyl, n-propyl, orphenyl; or together with R⁴ can form a five to ten membered cycloalkylor heterocyclic ring, with the carbon atom to which they are attached;and R⁴ is methyl, ethyl, n-propyl, or phenyl; or together with R^(3a)can form a five- to ten-membered cycloalkyl or heterocyclic ring, withthe carbon atom to which they are attached.
 33. The olefin metathesiscatalyst according to claim 21, wherein: M is Ru; n is 0; m is 0; R^(a)is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstitutedC₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄aryl or substituted C₅-C₂₄ aryl; typically R^(a) is methyl, ethyl,n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; R^(b)is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstitutedC₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄aryl or substituted C₅-C₂₄ aryl; typically R^(b) is methyl, ethyl,n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; orR^(a) and R^(b) are linked together to form a five or a six heterocyclicmembered ring with the sulfoxide group; X and Y are independently N; Qis a two-atom linkage having the structure—[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—; R¹¹, R¹², R¹³, and R¹⁴ are independentlyhydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; “s” and “t” are independently 1; R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstitutedheteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl,unsubstituted heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; R¹ is hydrogen and R² isunsubstituted phenyl, substituted phenyl or substituted 1-propenyl; orR¹ and R² are linked together to form an optionally substitutedindenylidene;

X³ and X⁴ are independently S; and R^(x), R^(y), R^(w) and R^(z) areindependently hydrogen, halogen, unsubstituted phenyl; or R^(x) andR^(y) are linked together to form an unsubstituted bicyclic orpolycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w)and R^(z) are linked together to form an unsubstituted bicyclic orpolycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y)and R^(w) are linked together to form an unsubstituted bicyclic orpolycyclic aryl or a substituted bicyclic or polycyclic aryl.
 34. Theolefin metathesis catalyst of claim 33, represented by the structure ofFormula (VIII)

wherein: R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl,tert-butyl, cyclohexyl or phenyl; R^(b) is methyl, ethyl, n-propyl,iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) andR^(b) are linked together to form a five or a six heterocyclic memberedring with the sulfoxide group; R³ is adamantyl, 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl,2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl,3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl; R⁴ is2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl,2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl,2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl,2,4-dimethylphenyl or 2-methyl-phenyl; R¹ is hydrogen and R² isunsubstituted phenyl, substituted phenyl or substituted 1-propenyl; orR¹ and R² are linked together to form an optionally substitutedindenylidene; R¹¹, R¹², R¹³, and R¹⁴ are independently C₁-C₆ alkyl orhydrogen; R^(x), R^(y), R^(w) and R^(z) are independently hydrogen,halogen, unsubstituted phenyl; or R^(x) and R^(y) are linked together toform an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together toform an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together toform an unsubstituted bicyclic or polycyclic aryl or a substitutedbicyclic or polycyclic aryl.
 35. A method of synthesizing an olefinmetathesis catalyst represented by the structure of Formula (B)

the method comprising contacting an olefin metathesis catalystrepresented by the structure of Formula (V)

with a PR^(d)R^(e)OR^(f) ligand at room temperature in an inert solvent,wherein: R¹ is hydrogen; R² is phenyl or 2-methyl-1-propenyl; or R¹ andR² are linked together to form 3-phenylinden-1-ylidene; R³ is2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, or 2-iso-propyl-6-methylphenyl; R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, or2-iso-propyl-6-methyl phenyl; X¹ and X² are independently Cl; R^(a) isunsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstitutedC₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄aryl or substituted C₅-C₂₄ aryl; R^(b) is unsubstituted C₁-C₁₀ alkyl,substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substitutedC₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl;or R^(a) and R^(b) are linked together to form a five or a sixheterocyclic membered ring with the sulfoxide group; R^(d) isunsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl orunsubstituted C₃-C₈ cycloalkyl; R^(e) is unsubstituted C₁-C₁₀ alkyl,substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀aryl, substituted C₃-C₈ cycloalkyl or unsubstituted C₃-C₈ cycloalkyl;and R^(f) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈ cycloalkyl.
 36. The method accordingto claim 35, wherein: R¹ is hydrogen and R² is phenyl; or R¹ and R² arelinked together to form 3-phenylinden-1-ylidene; R³ is2,4,6-trimethylphenyl; R⁴ is 2,4,6-trimethylphenyl; R^(a) is methyl;R^(b) is methyl; R^(d) is phenyl; R^(e) is phenyl; and R^(f) is phenyl,methyl, p-(OMe)phenyl, iso-propyl or ethyl.
 37. The method according toclaim 36, wherein: R¹ and R² are linked together to form3-phenylinden-1-ylidene; and R^(f) is phenyl.
 38. A method ofsynthesizing an olefin metathesis catalyst represented by the structureof Formula (D),

the method comprising contacting an olefin metathesis catalyst ofFormula (V),

with a ligand of formula

in an inert solvent, wherein: R¹ is hydrogen; R² is phenyl or2-methyl-1-propenyl; or R¹ and R² are linked together to form3-phenylinden-1-ylidene; R³ is 2,4,6-trimethylphenyl,2,6-di-iso-propylphenyl, or 2-iso-propyl-6-methyl phenyl; R⁴ is2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, or 2-iso-propyl-6-methylphenyl; X¹ and X² are independently Cl; R^(a) is unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl,substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substitutedC₅-C₂₄ aryl; R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl,unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; or R^(a) and R^(b)are linked together to form a five or a six heterocyclic membered ringwith the sulfoxide group; R^(k) is hydrogen, halogen, —NO₂, —CN, —CF₃,—SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; R^(l) is hydrogen,halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅,—NHC(O)OtBu, hydrocarbyl, substituted hydrocarbyl, heteroatom-containinghydrocarbyl, or substituted heteroatom-containing hydrocarbyl; R^(m) ishydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, or substituted heteroatom-containinghydrocarbyl; R^(n) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂,—NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; R^(s) is hydrogen or C₁-C₆ alkyl; andR^(q) is C₁-C₁₀ alkyl.
 39. The method according to claim 38, wherein: R¹is hydrogen and R² is phenyl; or R¹ and R² are linked together to form3-phenylinden-1-ylidene; R^(a) is methyl; R^(b) is methyl; R³ is2,4,6-trimethylphenyl; R⁴ is 2,4,6-trimethylphenyl; R^(k) is hydrogen;R^(l) is hydrogen; R^(m) is hydrogen; R^(n) is hydrogen; and R^(q) isiso-propyl.
 40. The method according to claim 39, wherein: R¹ and R² arelinked together to form 3-phenylinden-1-ylidene.